3MS: Multiphase Systems

Dr Daniele Vigolo

Room 117 – Chemical Engineering

Email: d.vigolo@bham.ac.uk
Tel: 0121 415 8694
Term 1 – schedule
 Mondays  lectures in LAW-LT1
11.00am – 1.00pm (week 2 – 6)
 Wednesday  tutorials in NUFF-G17
9.00am – 11.00am (week 3 – 6)

 Week 2 – 6: Dr Daniele Vigolo

 Week 7 – 10: Prof Mostafa Barigou
Key Textbooks
 ‘Introduction to Colloid & Surface Chemistry’, DJ Shaw, Butterworth
Heinemann, 2003.
 ‘Colloids and Interfaces with Surfactants and Polymers’, J Goodwin, Wiley,
2004.
 ‘Solid and Liquid Interfaces’, H Yildrim Erbil, Blackwell Publishing, 2006.
 ‘Basic Principles of Colloid Science’, DH Everett, Royal Society of Chemistry,
1988.
 ‘Foundations of Colloid Science’, RJ Hunter, Oxford University Press, 2001.
 ‘Understanding Rheology’, Morrison, 2001, Oxford Publishing, ISBN 0-19-
514166-0
 ‘An Introduction to Rheology’, Barnes, Hutton & Walters, 1989, Elsevier
Science, ISBN 0444874690
 ‘Rheology for Chemists: an Introduction’, 2000, Goodwin & Hughes.,
Cambridge: Royal Society of Chemistry, - ISBN 085404616x
 ‘Introduction to soft matter: synthetic and biological self-assembling materials’,
Hamley IW, 2007, John Wiley & Sons
Lecture 1: Introduction to
colloid & interface science
By the end of this lecture you will be able to:

 understand what a colloid is, give examples and describe how they
become unstable
 understand how surface molecules have different properties from the
bulk and are very important in colloidal systems
 understand the principles of Brownian motion from the Boltzmann
distribution and relate chemical potential as a driving force for
diffusion
 determine diffusion rates from first principles in the absence of gravity
 determine competing effects of gravity and diffusion in sedimentation
and creaming.
What is a colloid?
 A colloid is a substance in which microscopically
dispersed insoluble particles are suspended
throughout another substance.
 To qualify as a colloid, the mixture must be one
that does not settle or would take a very long time
to settle appreciably.
Types of colloidal dispersions

Discrete phase
Continuous Gas (bubbles) Liquid (droplets) Solid (particles)
Phase
Gas Not a colloid: Liquid aerosol Solid aerosol
solutions or molecular (fog, mist) (smoke)
dispersion
Liquid Liquid foam Emulsion Sol
(shampoo, whipped (milk, mayonnaise) (ink)
cream)
Solid Solid foam Solid emulsion Solid sol
(marshmallow, (butter) (ruby or stained glass)
packaging)
Important features
 Colloids consist of at least two phases comprising a
discrete or disperse phase and a continuous phase.
 The dispersed phase will be in the diameter range 1 nm to
1 m although some colloidal properties can be observed
up to 10 m.
 The surface-to-volume ratio is high for colloids - important
since surface molecules have different properties from the
bulk phase e.g. energy, molecular conformation.
The properties of the surface molecules are therefore of key
interest and these are different from the bulk! We cannot
describe such systems thermodynamically in terms of
summing contributions from bulk molecules
Important features
 Colloid and interface science is concerned with the
interfaces between liquids and solids, liquids and
gases and between solids and solids, liquids and
gases.
 Emulsion droplets may be larger than 1 m, the
wetting of solid surfaces and the adsorption of
gases may occur over large areas. These are topics
in interface science in which the length scale of the
interface is less than 1 m.
Colloid Stability
 Colloids can be classified as
lyophilic (solvent loving)
lyophobic (solvent hating)
 The terms hydrophilic and hydrophobic are used when
water is the dispersion medium.
 Similarly for oil, the term lipophilic refers to oil loving and
lipophobic to oil hating.
 The key feature of a colloid dispersion is that it is
thermodynamically unstable because of their high
surface free energy.
We will discuss how to stabilise later
Colloid Stability
Colloid Stability
Colloid Stability
 Instability leads to aggregation, which may evolve with
time. An initially formed rather open aggregate is termed a
floc and the process of formation is termed flocculation.
The floc may or may not separate out.
 If the floc rearranges to a denser form it is said to undergo
coagulation with the formation of a coagulum.
 An aggregate usually separates by a process of
sedimentation (if it is more dense than the dispersion
medium) or by creaming (if it is less dense than the
medium).
 Usually coagulation is irreversible whereas flocculation
may be reversed by a process of deflocculation.
Specific Surface Area
Typical values for a colloidal dispersion are 1 - 103 m2 g-1

Consider a cube of material with edges of length d correspond ing to a unit mass
so that the density is given by   m / v  1 / d 3  1 / v where m is the mass , v is the
volume and v is the specific volume or volume per unit mass :
Surface area 6 d 2 6
Specific surface area  As   
Unit mass d3 d
For a sphere of radius a and diameter d :
4 a 2 6
As  
4 a 3  / 3  d
The length scale in colloid
science
 Let’s look at how the proportion of molecules
at the surface of a particle changes as the
particle size decreases:
If the surface molecules have a linear di m ension h
and volume h 3 , the number per unit length of a cube of
the bulk with sides of length d is d / h  and the fraction
of molecules in the surface layer is :
Surface number 6 d / h  h
2
  6  
Total number d / h 3 d 
The length scale in colloid science
For a molar volume 0.05 nm3 (e.g. silver
bromide), h = 0.37 nm, thus:
• For a 1 cm cube, there are ~ 1 surface
molecules per 5 million.
• For a 1 m particle, ~ 1 in 500 molecules are
at the surface.
• For a 10 nm particle, ~ 1 in 5 molecules are at
the surface.
Moreover:
• Particles < 100 nm are called nanoparticles
and they have different properties to larger
colloidal particles.
• Particles < 1 nm would disperse such that the
equivalent of a solution would be formed.
Percentage of molecules in the
surface as a function of
particle size for a molar volume of 30
cm3 mol-1 (h = 0.37 nm).
Brownian Motion
 The attractive and repulsive forces between
colloid particles act over a similar length scale
of 0.1 - 0.5 m.
 When colloids are examined by optical
microscopy, the particles are observed to
undergo random motion - known as Brownian
motion after the botanist Brown who studied a
suspension of pollen grains in water.
Brownian Motion
 https://www.youtube.com/watch?v=R5t-
oA796to

 https://www.youtube.com/watch?v=Xscn-
QSmFo4
Brownian Motion

Random walk of (colloidal) particles due to Brownian motion

Brownian Motion – Drunkard's walk

Computer
simulation of two
random walks,
each of them made
up of 100 steps.

[R. Piazza, Soft Matter (Springer

Netherlands, Dordrecht, 2011)]
 Brownian Motion – Drunkard's walk

Final positions of 1000 drunkards after (from left to right) 100, 400
and 900 steps.
[R. Piazza, Soft Matter (Springer Netherlands, Dordrecht, 2011)]
The Boltzmann distribution and
definition of chemical potential
 Within a fluid, the molecules or particles have
a range of molecular interaction energies (due
to local repulsive and attractive forces) which
depend upon their local concentration in the
bulk.
 The energies and local concentration are
related by the Boltzmann distribution.
The Boltzmann distribution and
definition of chemical potential
Assume that the molecular interaction energy, μ, of a
specific molecule or particle (which we will assign the
letter j), has different values in two regions of a system
(e.g. vapour in equilibrium with a liquid).
The mole fractions of the species X1 and X2 (equivalent to
volume fractions in a gas) are thus determined as

 
X 1  X 2 exp  1j   2j / kT   
 X 1  then 1j   2j 
or : 1j  kT ln X 1   2j  kT ln X 2
The Boltzmann distribution and
definition of chemical potential
 k is the Boltzmann constant (1.381×10-23 J K-1). These
equations only apply to the dilute state and ideal mixing,
i.e. the mixing of the components does not cause the
overall volume to change.
 For n regions .

nj  kT ln X n  
.
 Molecules will diffuse between the regions until the above
is satisfied. To convert to per mole must multiply by
Avogadro’s constant NA = 6.022 × 1023 mol-1
Chemical potential
 Where µ is called the chemical potential (total free
energy per molecule including interaction energies).
This is on a per molecule basis. It is a form of potential
energy (PE) which can be absorbed or released due to
a chemical reaction or phase change. It is defined as
the gradient of the free (Gibbs) energy with respect to
the change in number of moles of that species i.e.

 G 
i   
 Ni T , P , N j ( i )
Dependence of chemical
potential upon concentration
 Activities, ai, are used to determine how chemical
potential of a species changes in a mixture or a
solution. The chemical potential is affected by
activity according to the following equation

i  i0  RT ln ai
 Activity is defined as
 i ci
ai  0
c
Diffusion as a result of chemical
potential (Brownian motion)

A m
c1  c2  x c1  c2  x 2

2 2x

c1  c2    dc
c1 c2 x dx

dm dc
  DA
Fick’s first law of
diffusion:
dt dx
x t  B x t 

x  2Dt 
1/ 2
Diffusion as a result of chemical
potential (Brownian motion)
 The mean displacement is thus proportional to
the square root of time. Now we relate the
diffusivity, D, to the chemical potential….
 A local variation in chemical potential will cause
particles to diffuse to try to equalise concentrations.
The one dimensional driving force is the derivative
of chemical potential with respect to x
d i
fd  
dx
Diffusion as a result of chemical
potential (Brownian motion)
 Now for an ideal system,

i  i0  R T ln ai  i0  R T ln ci

Ff d  
d
dx
 
i  R T ln ci  
0 R T d ci
ci d x

 Diffusion force per molecule

Fd kT d ci
fd  
NA ci dx
Diffusion as a result of chemical
potential (Brownian motion)
 This force is balanced by the viscous drag force of
the particle at its terminal diffusion velocity, ui.
fv  ui
 From Fick’s First Law
dm 1 dci
 ui ci   D
dt A dx

 Einstein-Smoluchowski relation kT
D

Diffusion as a result of chemical
potential (Brownian motion)
 For small particles (Re < 1), Stokes law applies. The
proof is lengthy, but the drag force for a sphere of
radius a can be written as
f v  6aui  3dui

 Thus   6a
 Stokes-Einstein relation D 
kT
6a
1
D

Settling under gravity
Buoyanc y Dra g
 As a particle or droplet settles Force Force
through a fluid, there are several
forces acting on it. When these
forces are in balance, the droplet
travels at a steady velocity, known
as the terminal velocity, ut.
 At equilibrium

f g  fb  fv
Gravity
Force
Settling under gravity
 The gravity and buoyancy forces can be expressed
respectively as
d 3  3
f g  md .a  d g fb  mc .a 
d
c g
6 6
d 3
 d   c g  ut
6

d 3 Stokes settling
d  c g  3dut d 2g
d  c   ut
6 18
Example
 Calculate the settling velocity (terminal
velocity) of a 2 µm particle in water. Over a
given characteristic time (say 1 second), how
far does it move relative to the mean distance
travelled by Brownian motion? What does
this tell you about gravitational
sedimentation?
 Settling and Creaming

fd  
d i
f d   f g  f b 
dz

d 3 d d ln c  z  h  h0 , c  c
  s   l  g   k T
6 dz dz z
z  h0  h c c
d 3
   s  l  g dz   k T d ln c  z  h 0 , c  c0
z  h0
6 c  c0
Settling and Creaming

z  h0  h c c
d 3
   s  l  g dz   k T d ln c 
z  h0
6 c  c0
z  h  h0 , c  c
z

 d 3 
c
 exp   s  l  hg / kT  z  h 0 , c  c0
c0  6 
Closure!
 understand what a colloid is, give examples and
describe how they become unstable
 understand how surface molecules have different
properties from the bulk and are very important in
colloidal systems
 understand the principles of Brownian motion from the
Boltzmann distribution and relate chemical potential
as a driving force for diffusion
 determine diffusion rates from first principles in the
absence of gravity
 determine competing effects of gravity and diffusion in
sedimentation and creaming.